201040221 六、發明說明： 【發明所屬之技術領域】 本發明是有關於-種橡谬組成物，特別是指 製備橡膠輥輪的橡膠組成物， ; 輪與其製備方法。 及應用其製得的一種橡勝輥 【先前技術】 以往製備橡膠組成物的過程中， 所要求的機械性質、财磨耗切酸㈣付0取終產 Ο Ο %㈣酸性等的標準，例如：要 =製備鋼板生產及加工工廠酸洗槽之絞乾輥輪的橡朦組 成物就必須具有财酸性等，多半會添加重 調整其性質。 日不 大陸公開號CN1701949A 一案中所揭示的汽車動力轉 向管的内管橡膠層和外管橡膠層令都含有二辛醋，其中， 該内管橡膠層是由由以下組份混煉而得的：氣續化聚乙稀 丁腈膠、氧化鎂、氧化鋅、促進劑、鉛丹、硫磺、硬脂 酸、噴霧碳黑、古馬龍及二辛醋等。然，近年來，隨著環 保意識抬頭，歐盟已將重金屬及二辛酯視為列管物質，故 為了符合環保標準，組成橡膠組成物的組份是必須要做調 整。 此外，CN100348656 —案所揭示一種超耐強酸橡膠材 料，其係含有以下重量份比的原料：7〇〜8〇份的氣磺化聚乙 烯、20〜30份的氯化聚乙烯、ι0〜15份的氟橡膠、2〜4份的 聚四氟乙烯、5~10份的甲基丙烯酸鋅、3〜6份的甲基丙烯 酸鎂、15〜60份的碳黑、5〜30份的填料、5〜2〇份的齊聚酯 201040221 、2〜3份的硫化劑及0.5〜2份的促進劑。此案雖然沒有使用 二辛酯，但是其所使用的氟橡膠單價貴，使得以此製得的 橡膠材料會有成本過高而不符合生產經濟效益的缺點，且 由說明書的實施例配方可知，通常還需要添加—氧化錯作 為硫化活化劑，而一氧化鉛是被歸為重金屬。 因此，仍有需要發展出一種具有良好性質、成本低且 不含歐盟列管物質的橡膠組成物。 【發明内容】 有鑒於環保要求而不能使用二辛酯，於是發明人藉由 多方尋免及測試’終於找到—種特有的不含苯環的二叛酸 一異壬S曰，並搭配經多次實驗而得的特定配方用量，進而 發展出&有良好性質、成本低且不含歐盟列管物質且適 用於製備橡膠輥輪的橡膠組成物。 因此本發明之第一目的，即在提供一種不含歐盟列 管物質且適用於製備橡膠輥輪的橡膠組成物。 於疋本發明用於製備橡膠輥輪的橡膠組成物係為一 包含一氯磺化聚乙烯膠 苯壞的二叛酸二異壬g旨 一丁腈橡膠、一硬脂酸、一不含 一填充劑及一硫化劑的混合物之 反應產物且以4氣續化聚乙稀膠與該丁腈橡膠總重量計 4氯κ化斌乙烯膠用量是介於丨〇 w伙至列评伐之間； «亥不3苯裒的—羧酸一異壬酯用量是介於1 wt%至丨5 之間；該填充劑用量是介於25 wt% s 75 wt%之間；該硫 化物用量是介於〇.5wt%至3wt%之間。 本發明之坌-a 弟一目的，即在提供一種具有良好性質、製 201040221 備成本低且不含歐盟列管物質的橡膠輥輪。 本發明橡膠輥輪係包含一圓柱狀軸桿，及至少一包覆 於該軸桿外周的橡膠層，且該橡膠層 组成物所構成的。 橡膠 本發明之第二目的，即在提供—種上述橡膠親輪的製 備方法。 本發明橡膠輥輪的製備方法係包含以下步驟：（a)對一 包含一氯磺化聚乙烯膠、一丁腈橡膠、一硬脂酸、一不含 〇 《環的二羧酸二異壬酿、-填充劑，及-硫化劑的混合： 施予-壓延處理，以得到-橡膠薄片，且以該氯續化聚乙 烯膠與該丁腈橡膠總重量計，該氣磺化聚乙烯膠用量是介 : 於10 wt%至90 wt%之間；該不含笨環的二羧酸二異壬酯 用1是介於1 Wt%至15 Wt%之間；該填充劑用量是介於25 wt%至75 Wt%之間；該硫化物用量是介於〇 5至3 wt Z之間，（b)對一圓柱狀軸桿施予一表面喷砂處理及一上底 漆處理，以得到一表面經處理的軸桿；（〇在該步驟（b)之表 Ο 面經處理的軸桿上塗佈一層接著劑，藉此使該步驟（a)之橡 膠薄片黏覆於該轴桿上，以製得一包覆有橡膠薄片的轴桿 :及（d)將該步驟（c)之包覆有橡膠薄片的轴桿置於一溫度介 於100 C至180°C之間的加熱裝置内，使橡膠薄片進行硫化 反應在該轴桿外周形成一橡膠層，以製得該橡膠輥輪。 本發明的功效在於：在製備橡膠組成物時，使用不含 苯環的二羧酸二異壬酯取代業界常使用的鄰苯二甲酸二辛 酯（dioctyl phthalate ;以下簡稱為DOP)，並搭配經多次實驗 201040221 而得的特定配方用量，進而以低成本製得一具有良好性質 、不含歐盟列管物質且適用於製備橡膠輥輪的橡膠組成物 ，故確實能達成本發明之功效。 【實施方式】 有鑑於現有的橡膠組成物無法同時滿足不含歐盟列管 物質，及具有適用於製備橡膠輥輪的良好性質，故發明人 測試多種不同的添加劑及不同組份用量，終於找出一種適 用於製備橡膠輥輪的橡膠組成物。 本發明用於製備橡膠輥輪的橡膠組成物係為一包含一 氣磺化聚乙烯膠、一丁腈橡膠、一硬脂酸、一不含苯環的 二羧酸二異壬酯、一填充劑及一硫化劑的混合物之反應產 物，且以該氯磺化聚乙烯膠與該丁腈橡膠總重量計，該氯 磺化聚乙烯膠用量是介於10 wt%至90 wt%之間；該不含 苯環的二羧酸二異壬酯用量是介於1 wt%至15 wt%之間； 該填充劑用量是介於25 wt%至75 wt%之間；該硫化物用 量是介於〇 · 5 wt%至3 wt%之間。 較佳地，該填充劑是選自於碳黑、白煙、（雙-(3-(三乙 氧基-硅烷基）-丙基）四硫化物），或此等之一組合。更佳地， 該填充劑為碳黑。 較佳地，該硫化劑是選自於硫磺、乙硫脲 (ethylenethiourea ;以下簡稱為ETU)、雙硫化四曱基硫代甲 醯胺（tetramethylthiuramdisulfide ;以下簡稱為 TMTD)、雙 硫苯°坐（benzothiazolyl disulfide;以下簡稱為DM)及雙五亞 曱基四石泉化硫代甲醯胺（dipentamethylene thiuramtetrasulfide 201040221 ;以下簡稱為TRA)，或此等之一組合。 較佳地，該混合物還包含一促進劑，該促進劑是選自 於活性氧化鎂、氧化辞，或此等之一組合。 較佳地，該混合物還包含一延遲劑，該延遲劑為一確 醢胺衍生物（sulfonamide derivative)。更佳地，該延遲劑是 選自於N-氧二乙稀-2-苯亞嗟β坐績醯胺（N-oxydiethylene-2-benzothiazyl sulfenamode)、N-環己基硫代鄰苯二甲亞胺（N-(cyclohexylthio) phthalimide) 5 或此等之一組合。 ^ 較佳地，該混合物還包含一防老劑，該防老劑為1,2 -二 氫-2,2,4-三曱基喧琳聚合物（丁1^1(^卩〇1}^11161^26(11,2-(11117(11*〇-2,2,4-trimethylquinoline)。 較佳地，該橡膠組成物係呈薄片狀。 本發明橡膠輥輪係包含一圓柱狀軸桿，及至少一包覆 於該軸桿外周的橡膠層，且該橡膠層是由如上所述之橡膠 組成物所構成的。 較佳地，該圓柱狀軸桿的材質是鐵。 〇 本發明橡膠輥輪的製備方法係包含以下步驟：（a)對一 包含一氯磺化聚乙烯膠、一丁腈橡膠、一硬脂酸、一不含 苯環的二羧酸二異壬酯、一填充劑，及一硫化劑的混合物 施予一壓延處理，以得到一橡膠薄片，且以該氯磺化聚乙 烯膠與該丁腈橡膠總重量計，該氯磺化聚乙烯膠用量是介 於10 wt%至90 wt%之間；該不含苯環的二羧酸二異壬酯 用量是介於1 wt%至15 wt%之間；該填充劑用量是介於25 wt%至75 wt%之間；該硫化物用量是介於0.5 wt%至3 wt 7 201040221 間’ (b)對—圚柱狀軸桿施予—表面喷砂處理及一上底 二Γ—表面經處理的轴桿;⑷在該步驟⑻之表 面、，、生處理的軸桿上塗備一屉垃装免丨 i怖層接者劑，藉此使該步驟（a)之橡 «片黏覆於該轴桿上，以製得—包覆有橡膠薄片層的轴 才干’及⑷將該步驟⑷之包覆有橡膠薄片層的軸桿置於一溫 度，I於_(：至i8(rc之間的加熱裝置内，使橡膠薄片進行 硫化反應在該軸桿外周形成一橡膠層，以製得該橡膠親輪 0 較佳地，該步驟（d)的溫度是介於140艺至16(rc之間。 實施例 本發明將就以下實施例來作進一步說明，但應瞭解的 是，該等實施例僅為例示說明之用，而不應被解釋為本發 明實施之限制。 <化學藥品> 1. loo%的純氯磺化聚乙烯膠（以下簡稱CSM):購自於杜邦 公司；型號為40 S。 2. 硬J!日酸·蹲自於.承德油脂；型號為stearic acid。 3. 白煙：購自於：台茂；型號為233-T。 4. 活性氧化鎂：購自於日本神島化學；型號為STARMAG-150 ° 5 ·乙硫脲、雙硫化四甲基琉代甲醯胺、雙硫苯唾及雙五亞 甲基四硫化硫代甲醯胺皆購自於富源化工。 6_ 丁腈橡膠（以下簡稱NBR):購自於南帝化工；型號為： NANCAR 1052。 201040221201040221 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a rubber composition, and more particularly to a rubber composition for preparing a rubber roller, a wheel and a method for preparing the same. And a rubber winch obtained by using the same method [Prior Art] In the process of preparing a rubber composition in the past, the required mechanical properties, the cutting power of the acid (4), the weight of the final product, the (% (4) acidity, etc., for example: To = prepare the steel sheet production and processing plant pickling tank, the rubber composition of the pickling roller must have a rich acidity, etc., and most will add weight to adjust its properties. The inner tube rubber layer and the outer tube rubber layer of the automobile power steering tube disclosed in the case of the Japanese Unexamined Publication No. CN1701949A contain dioctyl vinegar, wherein the inner tube rubber layer is obtained by mixing the following components. : Gas continuous polythene nitrile rubber, magnesium oxide, zinc oxide, accelerator, lead dan, sulfur, stearic acid, spray carbon black, coumarone and dioctyl vinegar. However, in recent years, with the rise of environmental awareness, the European Union has regarded heavy metals and dioctyl esters as listed substances, so in order to comply with environmental standards, the components that make up the rubber composition must be adjusted. In addition, CN100348656-the disclosure discloses a super-resistant strong acid rubber material containing the following raw materials by weight: 7〇~8〇 parts of gas sulfonated polyethylene, 20~30 parts of chlorinated polyethylene, ι0~15 Parts of fluororubber, 2 to 4 parts of polytetrafluoroethylene, 5 to 10 parts of zinc methacrylate, 3 to 6 parts of magnesium methacrylate, 15 to 60 parts of carbon black, 5 to 30 parts of filler, 5 to 2 parts of oligoester 201040221, 2 to 3 parts of vulcanizing agent and 0.5 to 2 parts of accelerator. Although the case does not use dioctyl ester, the fluororubber used therein is expensive, so that the rubber material thus obtained has the disadvantage of being too costly and not in conformity with the production economic efficiency, and it can be known from the formulation of the embodiment of the specification. It is usually also necessary to add - oxidization as a vulcanization activator, and lead monoxide is classified as a heavy metal. Therefore, there is still a need to develop a rubber composition that has good properties, is low in cost, and does not contain EU-listed substances. [Inventive content] In view of the environmental protection requirements, dioctyl ester could not be used, so the inventor searched and tested by the multi-party to finally find a unique benzene ring-free two-rebel acid-synthesis, and The specific formulation amount obtained in the second experiment, in turn, develops a rubber composition which has good properties, is low in cost, does not contain EU tubular substances, and is suitable for preparing a rubber roller. It is therefore a first object of the present invention to provide a rubber composition which is free of EU tubular materials and which is suitable for use in the preparation of rubber rolls. The rubber composition used in the preparation of the rubber roller of the present invention is a disulfonic acid diisoindole containing a chlorosulfonated polyethylene phthalate, a nitrile rubber, a stearic acid, and a non-one. The reaction product of the mixture of the filler and the vulcanizing agent and the amount of the 4 chloro-kappabin ethylene rubber in the total weight of the 4 gas-renewed polyethylene rubber and the nitrile rubber is between 丨〇w and the column The amount of the hexamethylene carboxylic acid monoisodecyl ester is between 1 wt% and 丨5; the filler is between 25 wt% and 75 wt%; the amount of the sulfide is Between 5% and 5% by weight. The purpose of the present invention is to provide a rubber roller which has good properties, is low in cost, and does not contain EU tubular substances. The rubber roller of the present invention comprises a cylindrical shaft and at least one rubber layer covering the outer periphery of the shaft, and the rubber layer composition is constituted. Rubber The second object of the present invention is to provide a method of preparing the above-mentioned rubber parent wheel. The preparation method of the rubber roller of the present invention comprises the following steps: (a) a p-chlorosulfonated polyethylene gel, a nitrile rubber, a stearic acid, and a disulfonium dicarboxylate containing no ring. Mixing of a brewing, a filler, and a vulcanizing agent: a feeding-calendering treatment to obtain a rubber sheet, and the gas sulfonated polyethylene gum is based on the total weight of the chlorine-renewed polyethylene rubber and the nitrile rubber The amount is between 10 wt% and 90 wt%; the dicyclodecyl dicarboxylate containing no stupid ring is between 1 Wt% and 15 Wt%; the amount of the filler is between Between 25 wt% and 75 Wt%; the amount of the sulfide is between 〇5 and 3 wt Z, (b) applying a surface blasting treatment and a primer treatment to a cylindrical shaft to Obtaining a surface treated shaft; (using a layer of an adhesive on the treated shaft of the surface of the step (b), thereby adhering the rubber sheet of the step (a) to the shaft The shaft is coated with a rubber sheet: and (d) the shaft coated with the rubber sheet of the step (c) is placed at a temperature between 100 C and 180 ° C. Device The rubber sheet is subjected to a vulcanization reaction to form a rubber layer on the outer periphery of the shaft to obtain the rubber roller. The effect of the present invention is to use a diphenyl isophthalate without a benzene ring in the preparation of the rubber composition. The ester replaces the dioctyl phthalate (hereinafter referred to as DOP) which is commonly used in the industry, and is matched with the specific formulation amount obtained by the repeated experiment 201040221, thereby obtaining a good property at a low cost and containing no The EU administers the substance and is suitable for the preparation of the rubber composition of the rubber roller, so that the effect of the present invention can be achieved. [Embodiment] In view of the fact that the existing rubber composition cannot simultaneously satisfy the EU-free substance, and has the application The good properties of the rubber roller were prepared, so the inventors tested a variety of different additives and different component amounts, and finally found a rubber composition suitable for the preparation of rubber rollers. The rubber composition system for preparing rubber rollers of the present invention. Is a gas-containing sulfonated polyethylene gum, a nitrile rubber, a stearic acid, a benzene ring-free diisodecyl dicarboxylate, a filler and a reaction product of a mixture of vulcanizing agents, and the amount of the chlorosulfonated polyethylene gum is between 10 wt% and 90 wt%, based on the total weight of the chlorosulfonated polyethylene gum and the nitrile rubber; The amount of the benzene ring-containing diisononyl dicarboxylate is between 1 wt% and 15 wt%; the amount of the filler is between 25 wt% and 75 wt%; the amount of the sulfide is between 〇 Between 5 wt% and 3 wt%. Preferably, the filler is selected from the group consisting of carbon black, white smoke, and (bis-(3-(triethoxy-silyl)-propyl) tetrasulfide. Or a combination of the above. More preferably, the filler is carbon black. Preferably, the vulcanizing agent is selected from the group consisting of sulfur, ethylenethiourea (hereinafter referred to as ETU), and tetrasulfide disulfide. Tetramethylthiuram disulfide (hereinafter referred to as TMTD), benzothiazolyl disulfide (hereinafter referred to as DM) and dipentamethylene thiuramtetrasulfide 201040221; TRA), or a combination of these. Preferably, the mixture further comprises an accelerator selected from the group consisting of activated magnesium oxide, oxidized words, or a combination thereof. Preferably, the mixture further comprises a retarding agent which is a sulfonamide derivative. More preferably, the retarding agent is selected from the group consisting of N-oxydiethylene-2-benzothiazyl sulfenamode and N-cyclohexylthiophthalate. An amine (N-(cyclohexylthio) phthalimide) 5 or a combination of these. ^ Preferably, the mixture further comprises an anti-aging agent which is 1,2-dihydro-2,2,4-trimethyl sulfonium polymer (Ding 1^1(^卩〇1}^11161 ^26(11,2-(11117(11*〇-2,2,4-trimethylquinoline). Preferably, the rubber composition is in the form of a flake. The rubber roller of the present invention comprises a cylindrical shaft, and At least one rubber layer coated on the outer circumference of the shaft, and the rubber layer is composed of the rubber composition as described above. Preferably, the cylindrical shaft is made of iron. The preparation method comprises the following steps: (a) a monochlorosulfonated polyethylene gum, a nitrile rubber, a stearic acid, a benzene ring-free diisononyl dicarboxylate, a filler, And a mixture of a vulcanizing agent is subjected to a calendering treatment to obtain a rubber sheet, and the amount of the chlorosulfonated polyethylene rubber is 10% by weight based on the total weight of the chlorosulfonated polyethylene rubber and the nitrile rubber. Between 90 wt%; the amount of the benzene ring-free diisononyl dicarboxylate is between 1 wt% and 15 wt%; the filler is used between 25 wt% and 75 wt% The vulcanization The dosage is between 0.5 wt% and 3 wt 7 201040221' (b) pair-cylinder shaft-surface blasting and one upper-bottom two-surface treated shaft; (4) in this step (8) The surface of the raw rod is coated with a drawer of a smear-free splicer, whereby the rubber sheet of the step (a) is adhered to the shaft to obtain a package. And the shaft coated with the rubber sheet layer is placed at a temperature, and the rubber sheet is placed in a heating device between rc and i8 (rc) The vulcanization reaction forms a rubber layer on the outer circumference of the shaft to obtain the rubber carrier 0. Preferably, the temperature of the step (d) is between 140 and 16 (rc). Embodiments of the present invention will be as follows The examples are further described, but it should be understood that the examples are for illustrative purposes only and should not be construed as limiting the invention. <Chemicals> 1. loo% pure chlorosulfonate Polyethylene rubber (hereinafter referred to as CSM): purchased from DuPont; model is 40 S. 2. Hard J! Japanese acid · 蹲 from. Chengde grease; model is steari c acid. 3. White smoke: purchased from: Taimao; model number is 233-T. 4. Active magnesium oxide: purchased from Shendao Chemical, Japan; model is STARMAG-150 ° 5 · ethylthiourea, sulfurized four The base carbamide, dithiobenzoate and bis-pentamethylene thiocarbamate are purchased from Fuyuan Chemical. 6_ Nitrile rubber (hereinafter referred to as NBR): purchased from Nandi Chemical; : NANCAR 1052. 201040221
. 7·鄰本一甲酸一辛醋·講自於聯成化學；型號為deHP (DOP)。 8. 不含苯環的二羧酸二異壬酯：購自於代理商首立；型號 為 NB-7。 9. 碳黑：購自於代理商極東貿易；型號為N_33〇。 10. 黏土：購自於：首立；型號為PF_216。 11. N-氧一乙浠-2-苯亞嗟嗤確酿胺：Monsanto(美國）製造； 型號為Santocure MOR ;下表2中以延遲劑3表示之。 o 12.N-環 己基硫代鄰苯二甲亞胺：Monsanto(美國）製造；型號 為Santoguard PVI ;下表2中以延遲劑b表示之。 13.1，2-二氫-2,2,4-三甲基喳啉聚合物：購自於川口化學；型 號為Antage RD ;下表2中以防老劑表示之。 硫化測試 一般在製備硫化橡膠輥輪前，會先利用組份相對簡單 的混合物進行硫化反應的測試，並利用一硫化儀（ Μ__ 2_)來判斷硫化程度，進而找到一組較佳的硫 〇 化條件’通常可以從硫化曲線中的MH、ML、_及ts2來 看，其中，ΜΗ是硫化曲線上的最高點，代表最高轉矩，可 由此看出樣品充分硫化後的剪切模量或剛度；ml是硫化曲 :上的最低點’代表最低轉矩，可由此看出未硫化前樣品 槎口占度，t90為達到MH_%時所需的時間，可以反應出 的正硫化時間；ts2為達到紙+2時所需的時間，可以 反應出樣品的焦燒時間。 案中發明人即是利用不同配方的硫化曲線上的 9 201040221 ΜΗ、ML、t90及ts2數值，進而找出一組硫化效果較佳的 混合物的組份種類及用量，如下表1的測試例1所示，表j 亦同時列出含有氧化鉛（pb〇)(購自於富源化工）及四氧化 三鉛（pb3〇4)(購自於富源化工）的測試比較例做性質比較 。需特別說明的是，由於碳黑的顏色較深，故為了便於觀 測硫化程度，本案發明人先使用白煙進行硫化測試。 表1 ----- ——'~--- 測試例1 測試比較 例1 測試比較 例2 CSM 100 100 1' ---- 1 0Π 硬脂酸 1 1 — _ 1 W U 1 白煙（233-Τ) 10 20 10 ΖηΟ 1 組份用量 活'14氧化鎂 8 2 10 PbO - 一 Γ 20 Pb304 - 1.5 ETU - 1.5 TMTD 2 - TRA - 〇 75 DM 硫續 1 1 r 硫化曲線 分析 ΜΗ (lb-in) 16.53 丄· 24.22 5 6 ML (lb-in) 0.73 1.34 1—- - 1 28 t90 (min) ts2 (min) 3QJA ~ 3 65 40.13 π π η 34.35 代表未添加。 u. /y 0.94 【註2】組份用量是以橡膠（即CSM)重量為1〇〇份為基準。 <實施例1〜3及比較例1 > [製備方法] 實施例1〜3及比較例1分別是先以依序使用一桌上型 捏合機（廠牌：富智儀器；機型為Table Kneader_pBV)及 10 201040221 . 一雙輥輪混煉機（廠牌：SCHWABENTHAN ;機型：直徑 6” X長度14”）將如下表2所示的配方混合均勻，即混煉 約8至10分鐘，以製得一橡膠組成物，再將該橡膠組成物 置於一溫度為160°C的加熱板上進行硫化反應，歷時1小時 ，進而製得一硫化橡膠。 [性質評估] 本案發明人分別參照不同的標準測試法中所述的操作 流程對實施例1〜3及比較例1之硫化橡膠各項性質評估， ❹ 其中，拉伸強度（kg/cm2)和伸長量（％ )是參照CNS3553 ;耐 磨耗（cc)是參照ASTM D4060 ;永久變形率（％ )是參照 CNS3560 ; ASTM#1油重變化（％ )、強酸重變化（％ )及強鹼 重變化（％)是參照CNS3562 ;硬度（shore A)是參照CNS3555 ;ASTM#1油的硬度變化（A)、強酸硬度變化（A)及強鹼硬度 變化（A)是參照CNS3555 ;密度是參照CNS5341，另，需 特別說明的是，上述所提及的強酸重及硬度的測試是將試 片在80°C的溫度下浸泡於30%的濃鹽酸内24小時，而強 Q 鹼是將試片在80°C的溫度下浸泡於30 wt%的氫氧化鉀内 24小時，並比對浸泡前後的重量及硬度的變化，結果如下 表2所示。 11 2010402217. Neighboring one-formic acid-octyl vinegar · Speaking from Liancheng Chemical; model deHP (DOP). 8. Diphenyl isophthalate dicarboxylate without benzene ring: purchased from the agent's first; model NB-7. 9. Carbon black: purchased from the agent Extreme East Trade; model number N_33〇. 10. Clay: purchased from: Shouli; model PF_216. 11. N-Oxo-Ethyl-2-pyrenequinone Amine: Made by Monsanto (USA); model number is Santoc MOR; Table 2 below is represented by retarder 3. o 12. N-Cyclohexylthiophthalimide: manufactured by Monsanto (USA); model is Santoguard PVI; Table 2 below is represented by retarder b. 13.1,2-Dihydro-2,2,4-trimethylporphyrin polymer: purchased from Kawaguchi Chemical; model number is Antage RD; Table 2 below shows it as an anti-aging agent. Vulcanization test generally uses a relatively simple mixture of components to test the vulcanization reaction before preparing the vulcanized rubber roller, and uses a vulcanizer (Μ__ 2_) to judge the degree of vulcanization, and then find a better set of sulfurization conditions. 'It can usually be seen from the MH, ML, _ and ts2 in the vulcanization curve, where ΜΗ is the highest point on the vulcanization curve, representing the highest torque, which can be seen from the shear modulus or stiffness of the sample after sufficient vulcanization; Ml is the sulphide: the lowest point on the ' represents the lowest torque, which can be seen as the sample sputum occupancy before unvulcanization, t90 is the time required to reach MH_%, the positive vulcanization time can be reflected; ts2 is the paper The time required for +2 can reflect the scorch time of the sample. In the case, the inventors used the values of 9 201040221 ΜΗ, ML, t90 and ts2 on the vulcanization curves of different formulations to find out the type and amount of the components of the mixture with better vulcanization effect, as shown in test example 1 of Table 1 below. As shown, Table j also lists the comparative comparisons of test cases containing lead oxide (pb〇) (purchased from Fuyuan Chemical) and lead trioxide (pb3〇4) (purchased from Fuyuan Chemical). In particular, since the color of the carbon black is deep, in order to facilitate the observation of the degree of vulcanization, the inventors of the present invention first used white smoke for the vulcanization test. Table 1 ----- ——'~--- Test Example 1 Test Comparison Example 1 Test Comparison Example 2 CSM 100 100 1' ---- 1 0Π Stearic acid 1 1 — _ 1 WU 1 White smoke (233 -Τ) 10 20 10 ΖηΟ 1 Component Usage '14 Magnesium Oxide 8 2 10 PbO - One Γ 20 Pb304 - 1.5 ETU - 1.5 TMTD 2 - TRA - 〇75 DM Sulfur Continued 1 1 r Vulcanization Curve Analysis ΜΗ (lb- In) 16.53 24.· 24.22 5 6 ML (lb-in) 0.73 1.34 1—- 1 28 t90 (min) ts2 (min) 3QJA ~ 3 65 40.13 π π η 34.35 means not added. u. /y 0.94 [Note 2] The component dosage is based on the weight of rubber (ie CSM) of 1 part. <Examples 1 to 3 and Comparative Example 1 > [Preparation method] Each of Examples 1 to 3 and Comparative Example 1 was sequentially used in a table type kneading machine (label: Fuzhi Instrument; model was Table Kneader_pBV) and 10 201040221 . A double roller mixer (label: SCHWABENTHAN; model: diameter 6" X length 14") The formulation shown in Table 2 below is evenly mixed, that is, mixing for about 8 to 10 minutes. To obtain a rubber composition, the rubber composition was subjected to a vulcanization reaction on a hot plate having a temperature of 160 ° C for 1 hour to obtain a vulcanized rubber. [Evaluation of properties] The inventors of the present invention evaluated the properties of the vulcanized rubbers of Examples 1 to 3 and Comparative Example 1 with reference to the operation procedures described in the respective standard test methods, 拉伸 where tensile strength (kg/cm 2 ) and elongation The amount (%) refers to CNS3553; the wear resistance (cc) refers to ASTM D4060; the permanent deformation rate (%) refers to CNS3560; ASTM#1 oil weight change (%), strong acid weight change (%) and strong alkali weight change (%) refers to CNS3562; hardness (shore A) refers to CNS3555; ASTM#1 oil hardness change (A), strong acid hardness change (A) and strong alkali hardness change (A) refer to CNS3555; density refers to CNS5341, In addition, it should be specially stated that the test of the strong acid weight and hardness mentioned above is to immerse the test piece in 30% concentrated hydrochloric acid at a temperature of 80 ° C for 24 hours, while the strong Q base is the test piece. The mixture was immersed in 30 wt% potassium hydroxide at a temperature of 80 ° C for 24 hours, and the changes in weight and hardness before and after the immersion were compared. The results are shown in Table 2 below. 11 201040221
」代表未添加或未測試。 組份用量是以橡膠（即CSM與NBR)總重量為1〇〇份為基準。 f備硫化橡勝輥輪 <應用例1 > 應用例1的製備步驟是先參照實施例1之橡膠組成物 12 201040221 的配方比例配置出約2.1 kg的未硫化橡膠組成物，再將其 交由包膠廠商進行小型橡膠輥輪成型試製，在進行包膠之 則，廠商會先準備一試驗鐵蕊（直徑為52 mm ;長度為15〇 mm)，並於包膠前一天進行鐵蕊表面喷砂及上底漆的塗糊作 業。 更進一步地說，本案係先進行包膠製程，並以14”輥筒 作業進行膠料混煉及出片，而貼膠作業則是於押出組以 2.5M貼膠機作業，其中，底層包膠厚度為6 mm，外層包膠 〇 厚度為8 mm，待貼膠完成後，再將該試驗鐵蕊置入一硫化 罐内，並以150C進行硫化反應4小時，接著，在靜置24 小時後，進行最終輪面粗車及表面研磨處理，進而製得一 . 表面粗糙度為0.54//m的小型橡膠輥輪。 綜上所述，本案在製備橡膠組成物時，以不含苯環的 二羧酸二異壬酯取代習知常用的二辛酯，如鄰苯二甲酸二 辛酯作為軟化劑，並將各組份限定於特定比例内，確實能 在不使用歐盟列管物質的情形下，仍可以低成本製得的具 0 ㈣合標準性質的橡膠組成物，因此，確實能達到本發明 之目的。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 13 201040221 【圖式簡單說明】 無 【主要元件符號說明】The representative was not added or not tested. The component usage is based on 1 part by weight of the total weight of the rubber (ie, CSM and NBR). f Preparation of vulcanized rubber winch <Application Example 1> The preparation procedure of Application Example 1 was to first arrange an unvulcanized rubber composition of about 2.1 kg with reference to the formulation ratio of the rubber composition 12 201040221 of Example 1, and then to give it The rubber rubber manufacturer is prefabricated by the rubber-clad manufacturer. In the case of rubber-clad, the manufacturer will prepare a test iron core (diameter 52 mm; length 15 〇mm) and iron core surface one day before the rubber coating. Sandblasting and primer application. Furthermore, in this case, the rubber coating process is first carried out, and the rubber compound is mixed and discharged by the 14" roller operation, and the glueing operation is performed by the 2.5M glue applicator in the extrusion group, wherein the bottom package The thickness of the rubber is 6 mm, and the thickness of the outer layer is 8 mm. After the glue is finished, the test iron core is placed in a vulcanization tank, and the vulcanization reaction is carried out at 150 C for 4 hours, and then, it is allowed to stand for 24 hours. After that, the final tread roughing and surface grinding treatment are carried out to obtain a small rubber roller having a surface roughness of 0.54//m. In summary, in the case of preparing a rubber composition, the benzene ring is not contained. The diisodecyl dicarboxylate replaces the conventionally used dioctyl ester, such as dioctyl phthalate as a softening agent, and limits the components to a specific ratio, and indeed does not use EU listing substances. In this case, the rubber composition having the standard property of 0 (four) can still be obtained at a low cost, and therefore, the object of the present invention can be achieved. However, the above is only a preferred embodiment of the present invention, and when In this way, the scope of the practice of the invention is defined, that is, The present invention and the scope of the invention described patent simple modifications and equivalent content made, the scope of the patent are still encompassed within the genus of the present invention. [FIG. 13 201 040 221 None of formula BRIEF DESCRIPTION OF REFERENCE NUMERALS main components